Print-out cyanine and styryl dye bases and process of producing litho masters and the like therewith



United States Patent 3,102,810 PRINT-OUT CYANINE AND STYRYL DYE BASESAND PROCESS OF PRODUCING LITHO MAS- TERS AND THE LIKE THEREWITH RobertH. Spragu'e, Chagrin Falls, Harry L. Fichter, Jr., Lakewood, and WilliamI. Hamilton, Cleveland, Ohio, assignors to Horizons incorporated, acorporation of New Jersey No Drawing. Filed Apr. 5, 1961, Ser. No.100,948

15 Claims. (Cl. 96-33) This invention relates to a non-silver directprint-out photographic system, sensitive to visible light, requiring nodevelopment and of sufficient speed to permit the use of a camera forthe taking of pictures.

The panchromatic photosystem of this invention is characterized by anenhanced speed due to a synergistic effect obtained by the use ofcombination of either (1) styryl bases or cyanine dye bases orcombinations of these in combination with (2) leuco bases or canbinolbases of triphenylmethane or djphenylmethane dyes, in photosysternsincluding organic halides represented by the generalizled formula A-CXwherein A is a monovalent radical selected from the group consisting ofH, Cl, Br, 1, alkyl (both substituted and unsubstituted) and aryl (bothsubstituted and unsubstituted), and each X is a halogen selected fromthe group consisting of Cl, Br and I, which generate free radicals onexposure to radiation of a suitable wavelength.

Preferably the photosystem also includes a suitable base material inwhich the light-sensitive material and the combination ofsynergistically acting agents are dispersed or on which they may besupported in the form of a thin film or coating.

As indicated above, in its simplest form the photosensitive system ofthis invention comprises the following:

(a) An organic halogen compound,

(15) One or more styryl dye bases, one or more cyanine dye bases ormixtures of the above,

(0) One or more leuco bases or carbinol bases of a triphenylmethane ordiphenylmethane dye, and

(d) A carrier which supports (a), (b) and (c) either as a dispersionthroughout the carrier or as an intimate admixture coated on a surfaceof the carrier material.

Each of the components of this photosensitive system and the manner inwhich the photosensitive system is utilized will now be considered ingreater detail.

(a) ORGANIC HALOGEN COMPOUND The organic halogen compounds suitable inthe photosystem of the present invention are those which release halogenfree-radicals when exposed to a proper dose of radiant energy and whichmay be represented by the generalized formula wherein A is a monovalentradical selected from the group consisting of H, Cl, Br, I,unsubstituted alkyl, substituted alkyl, unsubstituted aryl andsubstituted aryl.

Organic compounds which have been found suitable for the process includethe following compounds:

CBr, (carbon tetrabromide) HCBr (bromoform) C Br (hexabromoethane) C l-lCBr (benzotribromide) C HBr (pentabromoethane) Each of the abovecompounds yields a halogen freeradical when the bond joining a halogenatom to a polyhalogcnated carbon atom is ruptured upon exposure tolight. The presently preferred compound for this inven- 3,102,819Patented Sept. 3, 1963 (b) DYE BASE (l) Styryl Base The first of theseveral families of dye bases or dye progenitors, which constitutes oneof the synergists in the present photosystem, comprises the styryl dyebases and their higher vinylene homologs, such as those described in ourapplication Serial No. 42,233, filed July 12, 1960 issued as UnitedStates Patent 3,095,303 on June 25, 1963. As described in thatapplication, the variety of the colored styryl-base type compounds andtheir vinylene homologs is sufiiciently broad to blanket the visiblerange with respect to their light-absorption qualities and also withrespect to the nature of the color which can be produced as the resultof exposure to light when utilized in combination with organic halogencompounds of the type described above.

In view of the broad variety of dye bases available from the classindicated, it is possible in the present photosystem to expose ablue-sensitive variety to blue light to yield an intense yellow color, agreen-sensitive variety to green light to produce a magenta color, ared-sensitive variety to red light to produce a cyan color, etc. Thecolor of the developed image is thus complementary to the color of theexposing light, which is a necessary characteristic of a color negativematerial. The sharp cutting absorption, both of the progenitor and thecolor form produced as the result of exposure to light. is such thatincrements of absorption throughout the visible may be produced asdesired for specialized effects.

While we do not wish to be bound to any specific theory as to the reasonfor the ability to blanket the visible with respect to sensitivity anddevelopment of color, it appears that, either as a result of exposure tolight or possibly simply as the result of mixture of the organichalogen-containing compound and the weekly colored dye, a complex isformed which requires less energy to raise it to an excited state topermit the desired photolytic reaction to take place than when suchcomplexes do no form.

It has been pointed out that the dye progenitor is weakly colored and,as a result of exposure to light in the presence of the organic halogencompound, a brilliant, intense, sharp cutting color is obtained. Equallyimportant as the foregoing is our finding that, as a result of exposureto light with-or-without subsequent development by heat, a sharpdifference in solubility in certain solvents exists between unexposedand exposed areas. This finding is of exceptional importance in order toeliminate any residual color which may exist from the progenitor itselfand which might mask the desired print-out efiects. More important thanthe elimination of such color-masking effects is the fact that suchdifferences in solubility may be utilized for fixing and stabilizationof the printed image. Equally important is our finding that, as a resultof such solvent extraction, hydrophilic-hydrophobic differentiation isavailable, depending on whether or not the areas have been exposed tolight. Thus, it appears that the developed-out dye image is ionic incharacter, exhibits hydrophilic properties, and tends to be insoluble innon-polar solvents; whereas the unexposed dye progenitor, even in thepresence of the organic halogen-containing compound, is a covalentnon-ionic compound, soluble in a variety of organic solvents, and tendsto be hydrophobic in character. Such hydrophobic properties may beenhanced by placing the photosystem on a hydrophobic base. As aconsequence, the system can be utilized as a foundation of photoetchprocesses and as a means for producing a lithographic plate.

The present invcntion comprises an improvement over that described inthe aforesaid application, constituting the addition of a leuco base orcarbinol base of a trior diphenylmethane dye, whereby a greatly enhancedsensitivity is obtained.

Suitable styryl dye bases include two general types. The first is thestyryl base type obtained through the medium of aldehyde condensationreactions on heterocyclic bases containing an active methyl group, suchcondensation reactions being known to those skilled in the art. Thetypes of heterocyclic bases useful in such reactions include thefollowing:

Z-methylbenzothiazole Z-methylhenzimidazole Z-methylbenzoxazoleZ-methylthiazoline Z-methylbenzoselenazole 2-methyl-4-phenyloxazole2,3,3-trimethylindolenine Alpha-picoline Gamma-picoline QuinaldineLepidine l-methylisoquinoline S-methylisoquino-line2-methyl-a-naphthothiazole 2-methyl-B-naphthothiazole2,4-dimethylthiazole 2-methyl-4-phenylthiazole Z-methylthiazole2-methylthiopyranothiazole 2-benzothiazolylacetonitrileZ-quinolylacetonitrile 4-quinolylacetonitrile The second type of styryldye bases may be regarded as higher vinylene homologs of the styrylbases and may be obtained through the medium of condensation of theheterocyclic bases such as those listed above with cinnarnal types ofcompounds, again as known to those skilled in the art of the developmentof such color bases.

The styryl dye bases useful in the practice of this invention may berepresented by the following general formula:

wherein Rand R represent monovalent radicals selected from the groupconsisting of lower alkyl (i.e., methyl, ethyl, n-propyl) and benzyl,and may be the same as one another or different from one another; R"represents a :monovalent radical selected from the group consisting of Hand -CN; d and n each represents a positive integer which is either 1 or2; m is a positive integer not greater than 4; and the sum of n1 and m1is not greater than 4; and Q represents the nonmetallic atoms necessaryto complete a heterocyclic nucleus (ie, the atoms of C, O, 8, Se, and N)necessary to complete heterocyclic compounds such as those listed above.

(2) Cyam'nc Base The second of the several families of dye bases or dyeprogenitors, which constitutes one of the synergists in the presentphotosensitive system, comprises the cyanine dye bases such as thosedescribed in our pending application, Serial No. 95,031, filed March 13,1961.

The cyanine dye bases useful for the purposes of our invention are theseveral types, including those used commercially as supersensitizers inconventional silver halide photography. Although not themselves strongsensitizers, such bases impart increased sensitizing action to cyaninedyes when such combinations are employed in silver halide emulsions. Ingeneral cyanine dye bases are known corresponding to all the differentclasses of cyanine dyes, including symmetrical and unsymmetrical 1 IC2115 C1115 3,3'-diethylthiacarbocyanlne lodlde (12115 2-(3ethyl-23H)-henzothiazolylldeue)propenylbenzothiuzole Alternatively, cyanine dyebases are derived from heterocyclic bases by a wide variety of reactionswellknown to those skilled in the art. Typical heterocylic bases usefulin such reactions are the following:

Z-methylbenzothiazole Z-methylbenzoxazole Z-methylbenzimidazole2-methylthiazoline Quinaldine Lepidine l-methylisoquinolineZ-methyl-a-naphthothiazole Z-rnethyl-Bmaphthothiazole Alpha-picolineGamma-picoline 3-methylisoquinoline 2,4-dimethylthiazole2-methyl-4-phenylthiazole Z-methylthiazole 2, 3,3-trimethylindolenine2,4-dimethylselenazole Z-methylbenzoselenazole 2,4-dimethyloxazoleZ-methyLa-n aphthoxazole Z-methyl-fi-naphthoxazole2-methy1-4,S,6,7-tetrahydrobenzothiazole 2-methyl-4, 5,6,7-tetrahydrobenzoxazole Z-methyl-S,6,7,8-tetrahydro-4-cycloheptathiazole 2-methyl-5,6-dihydro-4-cyclopentathiazole 2-methyl-6,7-dihydro-4-H-pyrano 4,3D)thiazole Z-methyl-6,7-dihydro-4-H-thiopyrano(4,3D)thiazole2methyl-5,6-dihydro-4-H-pyrano( 3,2D)thiazole Z-cyanomethylquinolineZ-cyano-methylbenzothiazole 4-cyanomethylquinolineZ-cyanomethylbenzimidazole Z-cyanomethylpyridine 4-cyanomethyl pyridineCyanine bases useful in our novel photo process are characterized by thefollowing general formulas:

wherein d and e each represents a positive integer of from 1 to 2; nrepresents a positive integer of from 1 to 4; R represents an organicradical selected from the group consisting of alkyl, aralkyl and arylgroups; R represents hydrogen or a cyano group; and Q and Z eachrepresents the nonmetallic atoms necessary to complete 6 a heterocyclicorganic nucleus containing from 5 to 6 (D) atoms in the ring. S

Cyanine dye bases characterized by the above general formula may besymmetrical or unsymmetrical, of varying 1 C=CH- /N chain lengths; andthey may have substituents on the rings 5 or on the chain. Examples ofseveral types are depicted N below: (32% (1) Symmemcal ampa'mds 4-[(3-etl1yl-2 (3H) -benzothlazolylidene)methyl] qulnollne (A) 10Azacyanine bases useful in Our photoprocess may be regarded as relatedto the eyanine dye bases by replace- :CH CH:CH mer t by nitrogen of oneor more methine groups in the N N chain oining the two heterocyclicnuclei. They may be characterized by the following general formula:2-[3-(1-ethyl-2(1II)-quinolylldene)propenyflquinoline 1 Q Z (B) SR4610H=oH)d. C=(L-L)u-1=L-o 1cH-cH).-; N

l wherein d, e, n, R, Q and Z each has the same meaning as in generalFormulai above, and L represents a member N N 29 selected from the groupconsisting of CH and N and may 1 be the same or different, at least oneL being a nitrogen atom.

Typical azacyanine bases are listed below:

2- 2-methyl-3-(3-ethyl-2(3H)-benzothiazolylidene) propenyl]henzothiazole (o) (A) S W C=N-CH=CH 30 E 4-[(1-ethyl-2(lHyqulnolylldene)methyllquinollne 4 2- 3-ethy1 2 3H-benzothiazolylideneamlno) vinyl] quinoliue 2-[ 1-cyan0-5- 1 etl1yl-2(1H) -qu1nolylldene -1,3-pentadlenyl] C 2H5 qulnoltne 4-(1ethyl-2(1H)-qulnolylideneamin0)quinoline (E) (C) S o =NN=C H 0:0 HCH=CHCH==CHCH=CHO N \N N N I (i) H C 2H5 g 5 3-ethyl-2 (3H)benzothiaz0lylidene) (2-quinolylmethylene) 2- I 7- 3-etnyl-2 (3H)benzothlazolylidene) -1,3,5-heptatrienyl] hydrazine benzothiazole (D) SS (2) U nsymmetri cal Bases (A) c =NN=NC R 0 l C=CH-CH=CH \N/ l (3ethyl-2 (3H -benzothiazo1y1idene) (2-benzothiazolyllmino) hydrazine CM:(E) 2- 3- 3etl1yl-2 3H) -benzoxazolylldene propenyl] quinoline (B)C=CH-GH=CHCH=N- N N =CHC=CH N l E (3: 5 ,11 3 4-[(3-ethyl-2(3H)-benzoxazolylldene1-2-butenylideue] amlnoqulnoline4-[2-methyl-3 (l-ethyl-ZUH? -qu1nolyl1dene) propenyl] qulno the (F C N NC 11 E 4 6- 3-ethyl-2 3H -henzothmzolylldene) -2,4-hexadienylldene]aminoquinollne cyano d (3 ):n ld ny gafi iiil Gene) 3 A further class ofbases useful 1n our photoprocess are those containing nitrogen in thechain, related to the styryl dye bases and their vinylene homologs, andcorresponding to the following general formula:

2- (p-dlmethylaininobenzylidene aminoqulnollne 2-[(3-p-dimethylamtnophenyl)-2 propenylidene] aminobcuzohiazole 4-(p-dimethylnmlnophenylimino) cyanomethylquinoline CH N -N:N -N

C 4'(p-dimethylnminophenylazo) quinoline E GIIa N -N=C IIC H=C IIC II CH N\ CH:

4- 5-pdimethylamino-2.4-peutadlenylldene) aminopyridine In the samemanner as that in which the present invention comprises an improvementover Serial No. 42,233, filed July 12, 1960, it comprises an improvementover Serial N0. 95,031, filed March 13, 1961; that is, it provides aphotosystem of greatly enhanced sensitivity by the addition of a leucobase or a carbinol base of a triphenylmethane dye or a diphenylmethanedye to the photosensitive compositions described in our earlier filedapplication.

(0) LEUCO BASES OR CARBlNOL BASES OF TRIPHENYLMETHANE DYES OR DIPHENYL-METHANE DYES As compared with our earlier filed, above-notedapplications, the present photosystem achieves a vastly improvedsensitivity by virtue of the inclusion therein of a leuco base or acarbinol base of a triphenylmethane dye or of a diphenylmethane dye.

Suitable leuco bases or carbinol bases may be presented by one or theother of the following generalized formulae:

Leuco or carbinol base of triphenylmethane dye R; X B3 wherein R R R andR are each selected from the group consisting of H, alkyl, aralkyl andaryl groups and they may be the same or different, and R represents amonovalent radical selected from the group consisting of H and where Rand R have the same meaning as before and X is H for the leuco base andOH for the carbinol base. B. Leuco or carbinol base of diphenylmethanedye ;N -tH @N R: R4 wherein R R R and R have the same meaning as in theimmediately preceding formula (A, above) and X is again H for the leucobase and OH for the carbinvl base- (d) CARRIER A preferred method offormulating the photosensitive composition is to prepare a solution of afilm-forming plastic such as nitrocellulose in a solvent for theplastic, and to add the organic halogen compound (a) and the twosynergists (b) and (c) above to the solution. Cellulose derivatives suchas ethyl cellulose, methyl cellulose, carboxymethyl cellulose; syntheticpolymers such as polyvinyl chloride, polyvinylidene chloride (Saran),polyvinyl acetate; or any of a host of other carriers such as thosespecified in our earlier applications may be used.

(c) PROPORT'IONS In general, in the photosystems of the presentinvention, the principal constituent in the composition is the organichalogen compound. For each 1,000 parts by weight of the latter,approximately from 1 to 100 parts by weight of each of the synergistshas been found to produce particularly effective results, with about 2parts by weight of each yielding optimum increase in sensitivity.

To further illustrate the nature of the improvements obtainable with thephotosystem of the present invention, as compared with photosystems fromwhich the synergistic combination was absent, the following tablereports sensitivity for compositions consisting of 100 mg. of the dyebases listed below, mixed with 2.8 grams of CBr and dissolved in 16 ml.of 10% nitrocellulose in acetone. TABLE 1 Time in Seconds Wavelength(A.)

II III IV V I and II I I LCV 7O 30 (i5 3(] 5 75 30 (i5 5 7(] 25 65 25 36O 20 3 3O 30 15 3 45 40 40 15 5 80 25 7 150 190 45 l l 300 380 60 15180 75 16 200 .ltl 1.) 480+ 240 30 The data for the synergisticcombination of dye III and leuco-Crystal Violet are presentedgraphically as follows.

Leuco Crystal Violet Dye III (h-p-nmeth umm styryl Quinoline) E 45 DyeIII+Leuco Crystal :2 Violet 3S i5. a 33 3 3 g E2 2:.

as :2 I

s .3 I ,IllllrrrlinnnnnunlI:

3:00 420: 43cc 45cc use 4500 :00 5300 5500 e100 6 WavelengthA Thesolutions were coated on plastic film and exposed on a Bausch and Lombmonochromator at various wavelengths, using a slit width of 5millimeters and an exposure time sufiicient to give a reflection densityof I.

2 pdimethylaminostyryibenzothlazole 2- {4-( p-dimethylamlnophenyl)-1,3-butadienyl] quinoline CH3 N C H=C HC H=C II- N 6H34-i4(p-dimethylaminophenyl -1,3-butadienyl] qulnoiine LCV.-Leuco-CrystalViolet:

ILHCHs):

The examples which follow will serve to further illustrate thesensitivity obtained with compositions containing suitable amounts ofleuco bases or carbinol bases of triphenylmethane dyes anddiphenylmethane dyes.

EXAMPLE 1 When 50 milligrams of the styryl base,4-p-dimethylaminostyrylquinoline, and 50 mg. of the leuco base ofcrystal violet were dissolved in 16 cc. of ethyl acetate containing 2.8g. carbon tetrabromide, then coated on a clear or pigmented celluloseacetate substrate, excellent negative print-out images were obtained onexposure in a camera for thirty seconds at F45 in bright sunlight. Thedirect print image could be fixed by bathing in a solvent solutionconsisting of three parts ethyl acetate and seventeen parts benzene(3:17) to remove the unreacted starting materials.

EXAMPLE 2 Fifty milligrams of the styryl base,4-p-dimethylaminostyrylquinoline, and 50 mg. of Michlers hydro! weredissolved in a solution of 1.0% nitrocellulose in acetone containing 2.8g. carbon tetrabromide. The mix was coated on clear cellulose acetateand exposed through a negative to a General Electric sunlamp. Excellentprintout images were obtained on five and ten second exposures. Whenexposed in a camera at P45 in bright sunlight for in Example 1.

EXAMPLE 3 Fifty milligrams of the styryl base,Z-p-dimethylaminostyrylquinoline, and 50 mg. of Michlers hydrol weredissolved in 16 cc. ethyl acetate containing 1.4 g. of carbontetrabromide and coated on clear cellulose acetate. The resultingphotographic system gave excellent print-out images when exposed througha negative to a General Electric sunlamp for twenty seconds. The samemix with the styryl base omitted required twice that exposure for thesame image density, and with the Michlers hydrol omitted required sixtyto seventy seconds exposure for the same image density. The image wasfixed in the manner related in Example 1.

EXAMPLE 4 Fifty to 300 milligrams of the leuco base of Methyl Violetwere added to 16 cc. of ethyl acetate containing 2.8 g. carbontetrabromide and 50 mg. of 4-p-dirnethylaminostyrylquinoline. The mixeswere coated on cellulose acetate, and excellent images were seen on0.5-seeond exposure through a negative to a sunlamp. The same mixturewith the leuco base omitted required four seconds for an image of equaldensity, and with the 4-pdimethylaminostyrylquinoline omitted requiredtwo to four seconds for an image of comparable density. The images werefixed as in Example 1.

EXAM P LE 5 Fifty to 100 milligrams of the leuco base of Malachite Greenand 25 to 50 mg. of 4 p dimethylaminostyrylquinoline were mixed in 16cc. ethyl acetate containing 2.8 g. of carbon tetrabromide and coated oncellulose acetate. Excellent print-out images were obtained on one andtwo second exposures to a sunlamp through a negative. With leucoMalachite Green alone in the mix five to ten seconds exposure wasrequired for comparable images, and with only the4-p-dimethylaminostyrylquinoline in the CBr mixture, four seconds wasrequired for images of a like density. The images were fixed in themanner related in Example 1. When exposed in a camera in bright sunlightat P45, goo-d density negative print-out images were produced.

EXAMPLE 0 Fifty milligrams of the leuco base of Opal Blue Dye (C.I.42,760) and 50 mg. of 4-p-dimethylarninostyrylquinoline were dissolvedin 16 cc. ethyl acetate containing 2.8 g. carbon tetrabromide. Goodimages were formed on 0.5 to 4-second exposure to a sunlamp through anegative. The leuco base of Opal Blue alone required four minutes togive a reflection density of 1.0 when exposed on a monochromator at 3900A. and 4100 A., while in combination with4-p-dimethylaminostyrylquinoline only ten seconds exposure at thesewavelengths was required to give the same density. The4-p-dimethylaminostyrylquinoline alone in the above mix required athirty-second exposure to give density 1.0 at 3900 A. and 4100 A.Throughout the spectral range of 3900 A. to 4900 A. the presence ofleuco Opal Blue in combination with the styryl base gave a reflectiondensity of 1.0 twenty to thirty seconds faster than the same mix withoutleuco Opal Blue. Fixing was achieved in the manner described in Example1.

Films of this composition exhibited photosensitivity between 3900 A. and5700 A. as measured on a Bausch and Lomb 250-millimeter gratingmonochromator.

EXAMPLE 7 Twelve and one-half milligrams of 4,4'-methylene-bis(N,N-dimethylaniline) and 12.5 mg. of 4-p-dimethylaminostyrylquinolinewere dissolved in 8 cc. of ethyl acetate containing 1.4 g. carbontetrabromide and coated on clear transparent cellulose acetate sheets.When exposed to a 12 photofiood lamp, this coating produced densitiesmuch higher than either of the individual components of the mix for thesame unit of exposure, and, when the densities of the individualcomponents were superimposed one on the other, the combined density wasless than half that produced when both components were present in thesame mix.

EXAMPLE 8 Twelve and one-half milligrams of2-[4-(p-dimethylaminophenyU-l,3-butadienyllquinoline were added to 16cc. of 1% ethyl cellulose in toluene containing 12.5 mg. of the carbinolbase of the dye, Opal Blue SS (Cl. 42,760). To this mix was added 2.8grams of carbon tctrahromide, and the mixture was coated on polyvinylchloride sheets. When exposed on a Bausch and Lomb 250 rum-gratingmonochromator, this coating gave refiection density of 1.0 at exposuretimes of 17-25 seconds over the spectral range of 3900 A. to 4700 A.,while the 2-[4(p-dimethylaminophenyl) 1,3 butadienyflquinoline alonerequired l9-30 seconds over the same spectral range, and the czirbinolbase alone required 1l0 seconds for the same density over the samespectral range.

EXAMPLE 9 Twelve and one-half milligrams of4-(p-dimethylaminostyryl)quinoline, 25 mg. of2-[l-cyano-3(3-ethy1-2(3H)- benzoxazolylidene)-propenyl]quinoline(structure (a) below) and 1.0 mg. of leuco-Crystal Violet EXAMPLE 10Fifty milligrams of the azacyanine dye base, having the structure ([2)below and the chemical name,

I out,

2-[l3-ethyl 2(3H)-benzothiazolylidene)-ethylidene]aminobenzothiazole,and 25 mg. of leuco-Crystal Violet were mixed with a solution of 2.8grams of carbon tetrabromide in 16 ml. of a solution of 1% ethylcellulose in toluene. The mixture was coated on white Vinylite film andexposed under a negative to the light from a photoflood lamp. A fullyexposed print was obtained in ten seconds of a neutral gray-black color.A similar mixture from which the leuco-Crystal Violet was omitted gave amuch weaker image of approximately one-fifth the density, indicative ofa fivefold increase in speed, using the synergistic mixture.

In the claims which follow the expression lower alkyl is intended tocover straight and branched chain unsubstituted (saturated) alkyls withup to four carbons in the chain, namely methyl. ethyl, n-propyl, andisopropyl.

Having now described our invention in accordance with the patentstatutes, We claim:

1. A non-silver photosensitive composition which prints wherein R and Reach represents monovalent radicals selected from the group consistingof lower alkyl and benzyl; R" represents a monovalent radical selectedfrom the group consisting of H and -CN; d and n each represents apositive integer of from 1 to 2; m is a positive integer not greaterthan 4; and the sum of rz-l and m-l is not greater than 4; and Qrepresents the nonmetallic atoms selected from the group consisting ofC, O, S, Se, N, necessary to complete a heterocyclic ring with not morethan 6 atoms in the ring; cyanine dye bases represented by generalFormulas II and III below, wherein (-II) isR-N4CH=CH)a-r-b=(CH-OH)n-1=l- (CHCH),-| N wherein d and e eachrepresents a positive integer of from 1 to 2; n represents a positiveinteger of from 1 to 4; R represents an organic radical selected fromthe group consisting of alkyl, aralkyl and aryl groups; R represents amember of the group consisting of hydrogen and cyano groups; and Q and Zeach represents the nonmetallic atoms necessary to complete aheterocyclic organic nucleus containing from 5 to 6 carbon atoms in thering, and (III) is n-ri cH=oH).1.1 c=(LL ,=L- oH-on wherein d, e, n, R,Q and Z each has the same meaning as in general Formula II above, andeach L represents a member selected from the group consisting of CH andN, at least one L being a nitrogen atom, and styryl dye bases containingnitrogen in the chain and represented by the following general FormulaIV, and (IV) is R|\ x /R] )Gi G K R: X R; wherein R R R and R are eachselected from the group consisting of H, alkyl, aralkyl and aryl groups;X is selected from the group consisting of H and H and Y is selectedfrom the group consisting of H, phenyl, and

where R and R have the same meaning as before.

2. The composition of claim 1 dispersed in a clear, transparent solidfilm-forming plastic.

3. The composition of claim 2 as a self-supporting film.

4. A photosensitive article comprising the composition of claim 2 as acoating on a solid supporting substrate.

5. The composition of claim 1 wherein the organic halogen-containingcompound is CBr.;.

6. The composition of claim 1 wherein the organic halogen-containingcompound is CB the dye base is 4-(4-p-dimethylaminostyryl)quinoline andthe leuoo base is leuco-Crystal Violet.

7. The composition of claim I wherein the relative proportions of thephotolytically active organic halogencontaining compound, dye base andbase of an aryl methane dye selected from the group consisting of ieucobases and carbinol bases of diand tri-phenylmethane dyes are betweenabout 0.001 and about 0.01 part by weight each of dye base and of baseof an aryl methane dye selected from the group consisting of leuco basesand carbinol bases of diand tri-phenylmethane dyes for each part byweight of organic halogen-containing compound.

8. A process for producing colored photographic prints which comprisespreparing the composition of claim 1; coating a solid supporting surfacetherewith, exposing the composition to a colored subject, therebyproducing a negative image in color complementary to the coloredsubject.

9. The process of claim 8 wherein the image is intensi. fied by heatingfor between 1 and 10 seconds after exposure.

10. The process of claim 8 wherein the developed print is treated with asolvent to wash away the undecomposed dye base.

11. The process of claim 8 wherein a multilayer pack is prepared and afull color negative image complementary in color to the colored subject,is obtained.

12. A process for producing a full color positive image where a colornegative produced by the process of claim 11 is printed onto anothersheet of the same material.

13. The process of claim 8 wherein the permanence and brilliance of thecolor image produced is enhanced by treating the image with a metal saltsolution to form a lake.

14. The process of claim 8 wherein the substrate is paper and after thecolored image is produced, washing the developed image with water,drying the washed sheet, re-exposing the same with a blanket exposure,thereby producing a positive image of the subject.

15. A process for producing a litho master, comprising preparing thecomposition of claim 1; coating a caseinfilled paper therewith; exposingthe composition to light through a suitable negative, thereby producinga positive image in color; swabbing the exposed sheet with water torender the background ink-repellent, the image area then beingink-receptive.

References Cited in the file of this patent UNITED STATES PATENTS2,325,038 Chalkley July 27, 1943 2,702,242 Neugebauer et al Feb. 15,1955 2,835,576 Ensink May 20, 1958 2,855,303 Chalkley Oct. 7, 19582,855,304 Chalkley Oct. 7, 1958 3,033,677 Abbott et al. May 8, 19623,046,125 Wainer July 24, 1962 FOREIGN PATENTS 209,993 Germany May 14,1909 51,706 France Jan. 11, 1943

1. A NON-SLIVER PHOTOSENSITIVE COMPOSITION WHICH PRINTS OUT DIRECTLY ASA RESULT OF EXPOSURE TO VISIBLE LIGHT COMPRISING A MIXTURE OF THEFOLLOWING: (A) PHOTOLYTICALLY ACTIVE ORGANIC HALOGEN-CONTAININGCOMPOUNDS REPRESENTED BY THE GENERAL FORMULA A-C-BR3 WHEREIN A ISSELECTED FROM THE GROUP CONSISTING OF H, CL, BR, I, ALKYL, AND ARYL, (B)AT LEAST ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF STYRYL DYEBASED REPRESENTED BY GENERAL FORMULA I,
 15. A PROCESS FOR PRODUCING ALITHO MASTER, COMPRISING PREPARING THE COMPOSITION OF CLAIM 1; COATING ACASEINFILLED PAPER THEREWITH; EXPOSING THE COMPOSITION TO LIGHT THROUGHA SUITABLE NEGATIVE, THEREBY PRODUCING A POSITIVE IMAAGE IN COLOR;SWABBING THE EXPOSED SHEET WITH WATER TO RENDER THE BACKGROUNDINK-REPELLENT, THE IMAGE AREA THEN BEING INK-RECEPTIVE.